Wet abrasion resistant yarn and cordage

ABSTRACT

Aqueous overfinish compositions, yarns treated therewith, and methods of producing wet abrasion resistant cordage from the yarn are all disclosed. One of the compositions includes an oxidized polyethylene emulsified with a non-nitrogen, nonionic emulsifier and neutralized with an alkali hydroxide, and a compound selected from the group consisting of a siloxane of the comonomers dimethyl and 3-[(2-aminoethyl)aminopropyl], and an amide melamine wax. An alternate finish composition comprises an oxidized polyethylene, neutralized with ammonium hydroxide and emulsified with a non-nitrogen, nonionic emulsifier. Yarn treated with this alternate finish has enhanced wet abrasion resistance. Yarns of this invention are ideally suited for heavy ropes and other industrial cordage applications where wet and dry abrasion resistance and strength are desirable.

BACKGROUND OF THE INVENTION

1. Field of the Invention

The present invention relates to aqueous overfinish compositions, yarnstreated therewith and methods of producing wet abrasion resistantcordage from the yarn. More specifically, the present invention relatesto aqueous overfinishes for application to yarns of polyamide, polyesteror polyolefin to improve wet and dry abrasion resistance thereof as wellas that of cordage made therefrom.

2. Description of the Prior Art

Cordage products designed for prolonged contact with water need to havewet abrasion resistance. This invention is directed to enhancing wetabrasion resistance for cordage made from natural and/or syntheticfibers. The general term yarn is used herein to include mono- andmultifilaments, fiber, thread, yarn or other similar forms. Preferredare synthetic continuous filaments.

Cords or ropes fabricated of the yarns treated in accordance with theteachings of U.S. Pat. No. 3,103,448 to Ross are more resistant to wetand dry chafing abrasion. Drawn or undrawn synthetic continuous filamentyarns, especially nylon, are treated with an aqueous emulsion of anoxidized polyethylene (See U.S. Pat. No. 3,060,163 to Erchak, Jr.).Further, the coatings of oxidized polyethylene may be applied alone orwith other finish additives, e.g. silicones (column 3, lines 9-31).

Spin finishes for polyamide yarn which include an oxidized polyethyleneare disclosed in U.S. Pat. Nos. 3,917,893, 4,129,507, 4,293,460 and4,371,658, all to Marshall et al. An overfinish for polyester yarn whichincludes an oxidized polyethylene is disclosed in U.S. Pat. No.3,850,658 to Gomez et al.

Enhanced adhesion and fatigue resistance for polyester and polyamidetire and industrial yarns are achieved according to U.S. Pat. No.3,853,607 to Iyengar et al. via treatment with a lubricating finishcomposed of a polyorganosiloxane oil and a polyalkylene wax or amicrocrystalline wax dispersed in a dialkylphthalate oil. Known dressingagents (lubricants) for sewing threads are polydiorganosiloxane oils ora mixture of these oils and polyethylene waxes, according to U.S. Pat.No. 3,844,826 to Buchner et al., and U.S. Pat. No. 4,394,518 to Huber etal. states (column 3) that organosilicone compounds of that inventioncan be applied in admixture with other substances previously used toimprove slipping or gliding properties of organic fiber, e.g. paraffinand/or polyethylene waxes. Similarly, U.S. Pat. No. 3,983,272 to Huberet al. teaches improved lubricity or gliding ability of fibers bycoating with a composition containing a diorganopolysiloxane, aphosphorus compound and paraffin waxes. All of the prior art patentsmentioned above are hereby incorporated by reference.

None of the prior art teaches the required combination of ingredients toachieve the specific beneficial results of the finishes of thisinvention. More specifically, although it is known to use coatings ofoxidized polyethylene on yarn to improve wet and dry chafing abrasion,solids retention on the yarn (an indicator of durability of the coating)after prolonged exposure to water has been unsatisfactory with some ofthese coatings, and the wet abrasion resistance has not alwaystranslated to rope made of the yarn.

SUMMARY OF THE INVENTION

In accordance with this invention, there is provided an aqueousoverfinish for application to a yarn, preferably synthetic, comprisingan oxidized polyethylene, neutralized with ammonium hydroxide andemulsified with a non-nitrogen, nonionic emulsifier. Also in accordancewith this invention, there are provided yarns treated with theaforementioned composition and method of producing a wet abrasionresistant cordage therefrom.

Further, in accordance with this invention, there is provided a methodof producing a wet abrasion resistant cordage from yarn comprisingtreating the yarn, after drawing, with an effective amount of an aqueousoverfinish composition having an oil portion which comprises about 20 to80 weight percent of an oxidized polyethylene emulsified with anon-nitrogen, nonionic emulsifier and neutralized with an alkalihydroxide; and about 80 to 20 weight percent of a compound selected fromthe group consisting of a siloxane of the comonomers dimethyl and3-[(2-aminoethyl)-aminopropyl], and an amide melamine wax.

The synthetic yarns of the present invention preferably are chosen fromthe group of polyesters, polyamides and polyolefins. However, any yarnfor heavy duty cordage end use where the yarn (in rope/cord form) willget wet and need both wet abrasion resistance and strength iscomtemplated, e.g., towing, anchoring, hawsers, deep sea moorings,weighted net lines, marine usages.

The preferred polyesters are the linear terephthalate polyesters, i.e.,polyesters of a glycol containing from 2 to 20 carbon atoms and adicarboxylic acid component containing at least about 75 percent, morepreferably 90 percent terephthalic acid. The remainder, if any, of thedicarboxylic acid component may be any suitable dicarboxylic acid suchas sebacic acid, adipic acid, isophthalic acid, sulfonyl-4,4'dibenzoicacid, 2,8-dibenzofuran-dicarboxylic acid, or 2,6-naphthalenedicarboxylic acid. The glycols may contain more than two carbon atoms inthe chain, e.g., diethylene glycol, butylene glycol, decamethyleneglycol, and bis-(1,4-hydroxymethyl)cyclohexane. The most preferredlinear terephthalate polyester is poly(ethylene terephthalate).

Suitable polyamides include, for example, those prepared by condensationof hexamethylene diamine and adipic acid, condensation of hexamethylenediamine and sebacic acid known as nylon 6,6 and nylon 6,10,respectively, condensation of bis(para-aminocyclohexyl)methane anddodecanedioic acid, or by polymerization of 6-caprolactam,7-aminoheptanoic acid, 8-caprolactam, 9-aminopelargonic acid,11-aminoundecanoic acid, and 12-dodecalactam known as nylon 6, nylon 7,nylon 8, nylon 9, nylon 11, and nylon 12, respectively. Other suitablepolyamides include the aramids. The most preferred polyamide is nylon 6.

Suitable polyolefins include, for example, polyethylene homopolymer,polypropylene homopolymer, a polyethylene copolymer, and a polypropylenecopolymer. The polyethylene copolymer has at least 90 percent ethyleneunits and the remainder of the copolymer is a diluent such as propyleneor butylene. The polypropylene copolymer has at least 90 percentpropylene units and the remainder of the copolymer is a diluent such asethylene or butylene. Most preferred is the polyethylene homopolymer,commercially available from Allied Corporation as SPECTRA-900 orSPECTRA-1000.

The siloxane of the present invention is commercially available fromHenkel Corporation as Repellan 80, a siloxane of the comonomers dimethyland 3-[(2-aminoethyl)aminopropyl].

The amide melamine wax is formed by reacting melamine with a C₆ to C₃₆,more preferably C₁₀ to C₁₈, fatty acid to form a hydrophobic amide whichis emulsified with paraffin wax using nonionic emulsifiers; RepelotexHM, commercially available from Lyndal Chemical, is the wax of choice.

The oxidized polyethylenes utilized in the present invention are lowmolecular weight polyethylene homopolymers which have an averagemolecular weight of less than about 5000. The average molecular weightis the number average molecular weight determined by vapor phaseosmometry using phenetol as solvent. Preferably, the number averagemolecular weight is about 1000 to 4000 and most preferably about 1500 to2500. These polyethylenes have preferably been oxidized to an acidnumber of about 10 to 35, more preferably about 12 to 28 and mostpreferably about 13 to 17. These oxidized polyethylenes preferably havea softening point as determined by ASTM E-28 of about 85° to 145° C.,more preferably about 95° to 140° C. and most preferably about 98° to115° C. Preferably, such oxidized polyethylenes have a Brookfieldviscosity at 140° C. (284° F.) of about 120 to 300 centipoises(hereafter cps) and most preferably about 170 to 250 cps. Such oxidizedpolyethylenes are commercially available, for example, from AlliedCorporation as A-C® polyethylene type 680 and 392, the latter havingBrookfield viscosity at 149° C. (300° F.) of 9000 cps.

The oxidized polyethylenes useful in this invention may be obtained byoxidizing low molecular weight polyethylenes with air or oxygen byconventional procedures. See, for example, U.S. Pat. Nos. 3,060,163 toErchak, Jr., and 3,322,711 to Bush et al., as well as Canadian Pat. No.854 778, all of which are hereby incorporated by reference.

Any suitable non-nitrogen, nonionic emulsifying agent may be used inemulsifying the oxidized polyethylenes used in the present invention.Mixtures of higher fatty acids, for example, C₁₂ to C₂₀ saturatedaliphatic acids, may be used as emulsifiers as may also the alkylarylpolyether alcohols. Especially useful are the condensation products ofethylene oxide with hydrophobic material such as long chain aliphaticalcohol, acid, ester, ether or alkyl phenol. These products arecharacterized by containing as the hydrophilic portion of the molecule,a plurality of oxyethylene moieties as illustrated in the formulaebelow:

1. R--O--(CH₂ --CH₂ O)_(X) --CH₂ --CH₂ OH wherein R is an alkyl grouphaving from 12 to 22 carbon atoms or an alkyl phenol residue wherein thealkyl group contains from 6 to 13 carbon atoms inclusive and wherein Xis at least 4, especially between about 6 and about 40. Commercialexamples of products in this group include "Triton X-100" wherein R isan alkyl phenol residue wherein the alkyl group is isooctyl and whereinX is 7 to 9; "Triton X-102" wherein R is an isooctyl phenol residue andX is 11; "Tergitol NPX" wherein R is ethylhexyl phenol residue and X is8 to 9; "Neutronic 600" wherein R is nonyl phenol residue and X is 9;"Emulphor ELN" wherein R is dodecyl phenol residue and X is 19.

2. Condensation products of fatty acids in polyethylene glycols havingthe general formula:

    RCOO--(CH.sub.2 CH.sub.2 O).sub.X CH.sub.2 CH.sub.2 OH

wherein R is a long chain alkyl group having from 12 to 18 carbon atomsinclusive and X is an integer from 8 to 40 inclusive.

3. Polyoxyethylene derivatives of hexitol anhydride or sorbitol fattyacid esters such as "Tween 80".

4. Polyoxyethylene ethers

    R--O(CH.sub.2 CH.sub.2 O).sub.X CH.sub.2 CH.sub.2 OH

wherein R is an alkyl group having from 6 to 18 carbon atoms and X is aninteger from 4 to 40 inclusive. The preferred emulsifiers are the alkylphenols, most especially Triton X-100.

Alkali hydroxides suitable for use in the composition which includes thesiloxane or amide melamine wax include sodium hydroxide, potassiumhydroxide and ammonium hydroxide. The alkali hydroxide, preferably insolution, neutralizes the acid function of the polymer, i.e., theoxidized polyethylene, and is critical in making the polyethyleneemulsion and consequently, the finish.

In the alternate finish composition, ammonium hydroxide is critical inachieving enhanced wet abrasion resistance. In accordance with thisinvention, solids or finish retention of greater than 50 percent isachieved after prolonged exposure of the yarn to water, and dry and wetabrasion (tests defined hereafter) in excess of 200 and 100 cycles,respectively, can be achieved.

In the aqueous overfinish which includes the oxidized polyethylene andthe compound (either the siloxane or amide melamine wax) it is preferredthat the relative amounts of these compounds be about the same. At leastabout 0.25 weight percent of each of these on the yarn has been foundnecessary to achieve the beneficial results discussed. The aqueousfinish composition comprising an oxidized polyethylene neutralized withammonium hydroxide requires a minimum of 0.25 weight percent oxidizedpolyethylene on yarn; more preferably at least about 0.50 weight percentoxidized polyethylene on the weight of the yarn is put on the yarn.

BRIEF DESCRIPTION OF THE DRAWINGS

FIG. 1 is a front view of apparatus used in testing yarn to yarn wet anddry abrasion.

FIG. 2 is a side view of apparatus utilized to test yarn to metal wetabrasion.

DESCRIPTION OF THE PREFERRED EMBODIMENT

The preferred embodiment of this invention may be briefly stated asfollows:

An overfinish, particularly for continuous filament polyamide yarn to beprocessed into industrial cord, the finish being an oil in wateremulsion of about 15 to 30 percent by weight of the oil portion, the oilportion comprising about 20 to 80, most preferably 50, weight percent ofan oxidized polyethylene having an acid number of about 13 to 17 and asoftening point of about 98° to 115° C., emulsified with a non-nitrogennonionic emulsifier, preferably POE (9-10) nonyl phenol, and neutralizedwith sodium or potassium hydroxide; and about 80 to 20, most preferably50, weight percent of a compound selected from the group consisting of asiloxane of the comonomers dimethyl and 3-[(2-aminoethyl)aminopropyl],and an amide melamine wax formed by reacting melamine with a C₆ to C₃₆,preferably C₁₀ to C₁₈, fatty acid to form a hydrophobic amide which isemulsified with paraffin wax using nonionic emulsifiers. An alternatebut equally preferred embodiment of the invention is briefly stated asfollows: a finish for enhanced solids retention and wet abrasionresistance, particularly for continuous filament polyamide yarn to beprocessed into cordage products, the finish being an oil in wateremulsion of about 15 to 30 percent by weight of the oil portion, the oilportion comprising an oxidized polyethylene having an acid number ofabout 13 to 17 and softening point of about 98° to 115° C., neutralizedwith ammonium hydroxide and emulsified with a non-nitrogen, nonionicemulsifier such as POE (9-10) nonyl phenol.

The oxidized polyethylene wax as described may be emulsified in water byknown methods using any suitable emulsifying agent as set forth above.Reference may be had to U.S. Pat. Nos. 3,850,658 to Gomez et al. and4,371,658 to Marshall et al., both of which are hereby incorporated byreference, for methods of preparing aqueous emulsions of the oxidizedpolyethylenes.

In the examples, the commercially available polyethylene emulsions arediluted with water followed by blending with the other commerciallyavailable emulsion, all at room temperature, to achieve the desiredpercent solids. Concentrations of between about 2 and 40 percent solidsare suitable, and between about 5 and 15 percent are preferred.

The finish is applied to the yarn in any of the conventional manners. Asatisfactory way of applying the coating is by feeding the emulsion to atrough equipped with a rotatable roll dipping therein; the yarn contactsthis roll at a relative speed with respect to the rate of rotation ofthe roll adjusted to provide the desired pickup of coating by the yarn,for example, between about 3 and 8 percent pickup of the liquid coatingby weight based on the weight of the yarn.

The quantities of solids on yarn desired, i.e. between about 0.25 and0.80 percent by weight of the finished yarn, is sufficiently large thatthe solids need to be put on in an overfinish rather than spin finish.

The tests for yarn to yarn dry abrasion, yarn to yarn wet abrasion andyarn to metal wet abrasion are set forth as follows:

1. YARN TO YARN (Y/Y) DRY ABRASION TEST

With reference to FIG. 1, a one meter length of yarn 10 is tiedeccentrically at one end to a cycling wheel 9. Its other end is passedover a first free-wheeling yarn guide 11 and under a pulley 12, thenceover a second free-wheeling yarn guide 13, under a cut off device 14 andfinally over a third free-wheeling yarn guide 15. At its extreme, aweight 16 is tied onto the yarn. The yarn is looped prior to its beingplaced around pulley 12 to create twist point 17. The cycling wheel 9 isturned on to rotate clockwise; the yarn alternately is pulled toward thecycling wheel 9 and towards the weight 16 to exert an abrading action onthe yarn itself at the point of twist 17 above the pulley 12. Theresults are reported in cycles to break; the larger the number, thebetter the dry abrasion resistance. In Examples 1-23, weight 16 is equalto the nylon yarn denier of 1260. In Examples 42-46, weight 16 is asspecified in Table 6.

2. YARN TO YARN (Y/Y) WET ABRASION TEST

This test is identical to the dry abrasion test except that pulley 12with yarn 10 looped thereabout and twist point 17 are submerged in waterin container 18. Results are also reported in cycles to break with thelarger numbers being indicative of better wet abrasion resistance.

3. YARN TO METAL (Y/M) WET ABRASION TEST

Breaking strength is measured as taught by ASTM D-885-81, herebyincorporated by reference, with a 10-inch (25 cm) gage, 12-inch (30 cm)crosshead and 0 chartspeed (no stress strain curve). With reference toFIG. 2, a length of yarn 10 (about 1 meter) is taped at one end to thesurface of a cycling drum 20. Its other end is passed partially alongthe circumference of drum 20, through sponge 21, and over a stainlesssteel hexagonal bar 22 having a diameter of 0.25 inch (0.64 cm). At itsextreme, a weight 23 is tied onto yarn 10. In Examples 29-33, weight 23is 150 grams. Sponge 21, which sits in a canister 24 of water, ispartially slit from its top to an aperture (above the top of canister)through which yarn 10 passes. Drum 20 is caused to move back and forthin the direction of yarn travel enough to cause approximately 12 to 14inches (30-35 cm) of yarn 10 to be dragged back and forth over hexagonalbar 22 2500 times/cycles. As yarn 10 passes through sponge 21 duringcycling, it is wettened and wiped. After yarn 10 dries, its breakingstrength is again measured in accordance with ASTM D-885-81 above. Thebreaking strength retention in percent is determined and is set forth inTable 4 as the yarn to metal wet abrasion. This figure is arrived at bytaking the difference between the breaking strengths before and aftercycling, dividing the difference by the breaking strength beforecycling, and multiplying the resulting number by 100.

The yarns of this invention are especially adapted for fabrication intoropes of unusually high strength by well known commercial processes.Ropes are prepared from such yarns by a multistage process, the steps ofwhich may vary somewhat depending on the type of rope desired. Fortesting purposes, the ropes are prepared as follows:

The rope has a diameter of about 0.5 inch (1.3 cm) and comprises abraided core with a braided cover (Parallay® braid of Samson). The coreis made of 1260 denier--6 ply, 2 ends per carrier, 20 strand braider, at4.557 ppi (picks per inch), 3.072 pounds/100 feet (target). The cover ismade of 1260 denier--12 ply, 2 ends per carrier, 8 strands by 2, 24 endstotal, at 1.678 ppi, 3.421 pounds/100 feet (target). For testing, therope is passed at an angle of 10° and under 1700 pound load over acurved bar and cycled [18 inch (46 cm) span] until the braid breaks,under both wet and dry conditions. Results are reported in cycles tobreak; the larger the number the better the abrasion resistance. Withreference to Table 6, testing was done under quality control proceduresof a customer-break and elongation testing were performed with referenceto ASTM D-885 and linear density testing was performed with reference toASTM 1907. The test equipment used for break and elongation testing wasan Instron Model 1000.

The following specific examples further illustrate our invention. Partsare by weight except as otherwise noted.

EXAMPLES 1-23

1260 Denier polyamide yarn substantially as characterized in Example 1of U.S. Pat. No. 4,293,460 to Marshall et al. was made using a coupledor continuous spin draw unit. The 24 percent oil in water emulsion wasformed with the oil portion containing 55 percent rearranged glyceride,25 percent POE (9) oleyl alcohol, 15 percent POE (5) castor oil, and 5percent POE (9) nonyl phenol. The spin finish was applied to the yarnvia a kiss roll at a wet pickup level which was sufficient to add 0.7 to0.9 percent total spin finish on the weight of the fiber. In Example 1(control), no overfinish was applied to the yarn. In Examples 2-23, theoverfinishes designated in Table 1 were applied at a wet pickupsufficient to add on 0.5 percent solids on the weight of the yarn. Yarnto yarn wet and dry abrasion test results (6 tests per sample) andfinish retention data (1 test per sample) are presented in Table 1.Particularly excellent results were obtained in Examples 7, 15 and 22wherein yarn to yarn wet abrasion exceeded 140 cycles, yarn to yarn dryabrasion exceeded 300 cycles and finish retention exceeded 50 percent.

Note that when polyethylene emulsion alone is used as an overfinish(Examples 2, 3, 17, 19 and 22), the alkali hydroxide used to neutralizethe acid function of the polymer is critical. In Examples 2 and 3(sodium hydroxide neutralized), finish retention is significantlyinferior to Example 22 (ammonium hydroxide neutralized), and wetabrasion resistance is inferior to the control for Example 2 and onlymarginally better in Example 3. Example 22 is significantly better thanthe control. Similarly, Examples 17 and 19 (potassium hydroxideneutralized) have significantly inferior finish retention as comparedwith Example 22 (ammonium hydroxide neutralized) as well as a wetabrasion resistance inferior to the control.

EXAMPLES 24-28 (Comparative)

1260 Denier polyamide yarn was made substantially in accordance withExample 1 of U.S. Pat. No. 4,293,460 to Marshall et al. The overfinishesset forth in Table 2 were utilized as spin finishes in Examples 24-28.The emulsions were 20 percent oil in water emulsions added via a kissroll to achieve a wet pickup of 0.7 to 0.9 percent solids on yarn. Itwas then attempted to heat and dry the yarn on a conventional draw twistmachine. Draw twist completes, in percent, were determined for each ofExamples 24-28. The percent draw twist completes was unacceptably lowfor all except control Example 24, which had substantially less (about0.1) oxidized polyethylene on the fiber being processed.

EXAMPLES 29-36 (Comparative)

Example 1 was repeated utilizing the following spin finish: 55 partstransesterified coconut oil-glycerol trioleate, 25 parts POE (9) oleylalcohol, 15 parts POE (5) castor oil, 5 parts POE (9) nonyl phenol, and3.75 parts oxidized polyethylene. The first four components were blendedand emulsified. The oxidized polyethylene was emulsified separately andadded to the finish emulsion. This is the spin finish of Example 29. ForExamples 30-32, a 38 percent Repellan in water emulsion was then blendedwith the finish emulsion so that the Repellan represented from about 5to 15 percent of the oil phase (to achieve about 0.05 to 0.15 percentRepellan on fiber as designated in Table 3, 24 percent oil in wateremulsion). In Examples 33-35, the level of Repellan on yarn was heldconstant at 0.10 weight percent and the formulation varied to achievethe levels of polyethylene on yarn designated in Table 3. Test resultsfor yarn to metal abrasion and yarn to yarn wet abrasion are presentedin Table 3. Yarn test results were good.

In Example 36, an 840 denier polyamide yarn was formed. Duringformation, the yarn was treated with a spin finish comprising 1.58percent Discosoft 567 (19 percent solids, Footnote 12, Table 1),7.89percent Repellan 80 (38 percent solids, Footnote 11, Table 1), 24percent oil portion of Example 1 spin finish, and 66.53 percent water.Wet pickup was 5 percent to achieve 0.15 percent oxidized polyethyleneon yarn and 0.03 percent siloxane on yarn. Excellent draw twistcompletes, in percent, were achieved (96 percent).

EXAMPLES 37-41

In Examples 37-41, 1260 denier yarn formed with the finish systemsdesignated in Table 4 were made into rope (double braid construction)and tested for wet and dry breaking strength and retention, as well aswet and dry abrasion. Cordage made from yarn treated with theoverfinishes of Examples 7, 15 and 22 (Examples 37, 38 and 39 here) hadexcellent wet and dry abrasion resistance, while cordage made from yarntreated with the spin finish of Example 36 (Example 41 here) had asignificantly lower improvement in wet abrasion resistance when comparedwith the control of Example 40.

EXAMPLES 42-46

1000 Denier yarn was made substantially in accordance with Example 3 ofU.S. Pat. No. 3,850,658 to Gomez et al. The spin finish of Table 5 wasapplied to the undrawn polyester yarn at a rate of approximately 0.5percent to achieve 0.2 percent on fiber weight of the oil. After thedrawing step, the overfinishes designated in Table 6 were applied inExamples 42-46, respectively. The yarn was tested for yarn to yarn wetand dry abrasion, yarn to metal wet abrasion, and finish retention.Results are set forth in Table 6. Yarn wet abrasion resistance andfinish retention for Example 42 (sodium hydroxide neutralized oxidizedpolyethylene) were significantly inferior to Examples 44-46 of thepresent invention (note that Example 46 contains ammonium hydroxideneutralized oxidized polyethylene).

Although excellent abrasion resistance was achieved in Examples 43-46,the low finish retention of Example 43 leads one to suspect that theenhanced abrasion resistance of the yarn would not translate to acordage product.

EXAMPLES 47-50

A 118 filament polyethylene yarn is prepared substantially by the methoddescribed in U.S. Pat. No. 4,413,110 to Kavesh et al., herebyincorporated by reference. In Examples 48-50, the overfinishes ofExamples 7, 15 and 22, respectively, are applied with a wet pickupsufficient to achieve approximately 0.5 percent solids on fiber weight.It is anticipated that wet and dry abrasion resistance and finishretention will be significantly improved as compared with the control ofExample 47.

                                      TABLE 1                                     __________________________________________________________________________    NYLON OVERFINISH DATA                                                                                      Y/Y Abrasion, Cycles                                                                     Finish                                Example                                                                            Formulation.sup.1       Wet   Dry  Retention, %.sup.2                    __________________________________________________________________________     1   No overfinish            29   246  22                                    (control)                                                                      2   Polyethylene.sup.3 emulsion                                                                            15   452  27                                     3   Polyethylene.sup.4 emulsion                                                                            36   452  20                                     4   Paraffin wax.sup.5      148    33  --                                         (melts at 54.4° C.) + zirconium acetate                                (4.5% of 39% solids dispersion)                                           5   Paraffin wax.sup.5      165   196  27                                         (melts at 54.4° C.)                                                6   Amide melamine wax.sup.6 , 25% solids                                                                 136   284  35                                    *7   Amide melamine wax.sup.6 ,                                                                            190   452  51                                         25% solids + polyethylene emulsion.sup.7                                  8   Paraffin wax.sup.8      107   452  35                                         (melts at 60° C.) + aluminum acetate (4-5%)                        9   Paraffin wax.sup.8 (melts at 60° C.)                                                           128   452  38                                    10   Polyethylene, acrylic acid copolymer.sup.9                                                             8    452  --                                    11   Polyethylene, acrylic acid copolymer.sup.10                                                            24   452  --                                    12   Polypropylene wax        28    42  --                                    13   Paraffin wax.sup. 5     155    7   --                                         (melts at 54.4° C.) + polyethylene.sup.3                          14   Example 4 formulation + polyethylene.sup.3                                                            127    3   --                                    *15  Siloxane.sup.11 + polyethylene.sup.12 blend                                                           144   304  97                                    16   Dimethylpolysiloxane     6     2   --                                         (350 cts viscosity) silicone oil emulsion                                17   Polyethylene.sup.13 emulsion                                                                           12   165  --                                    18   Blend of formulations of Examples 5 and 17                                                            189    27  --                                    19   Polyethylene.sup.14 emulsion                                                                           18   228  --                                    20   Blend of formulations of Examples 5 and 19                                                            153    3   --                                    21   Dimethylpolysiloxane     5     2   --                                         (50 cts viscosity, nonaqueous)                                           *22  Polyethylene.sup.7 emulsion                                                                           149   452  91                                    23   Emulsion with solids content: 55 parts                                                                 10   452  --                                         transesterified coconut oil-glycerol trioleate;                               25 parts POE (9) oleyl alcohol; 15 parts POE (5)                              castor oil; 5 parts POE (9) nonyl phenol; and 15                              parts Discosoft 567.sup.12                                               __________________________________________________________________________     Footnotes                                                                     .sup.1 All formulations 10% solids in water emulsions for application         except Examples 21 (100%) and 23 (22%).                                       .sup.2 After 1 hour scour. Use 20 g sample of overfinished yarn.              Gravimetrically extract with cyclohexane to get level of finish on yarn.      Submerge a new 20 g sample in room temperature (about 25 to 30°        C.) water with constant stirring for 1 hour. Take out sample and allow to     air dry. Do a gravimetrical extraction. Compare the first and second          extractions as follows to determine finish retention:                         ##STR1##                                                                      .sup.3 AC ® polyethylene 680, commercially available from Allied          Corporation; oxidized polyethylene having an acid number of about 16 and      softening point of about 110° C.; neutralized with sodium              hydroxide.                                                                    .sup.4 A-C ® polyethylene 392, commercially available from Allied         Corporation; oxidized polyethylene having an acid number of about 28 and      softening point of about 138° C.; neutralized with sodium              hydroxide.                                                                    .sup.5 Repelotex D, commercially available from Lyndal Chemical.              .sup.6 Repelotex Hm, commercially available from Lyndal Chemical; melamin     reacted with a long chain fatty acid (e.g., C.sub.10 to C.sub.18 ) to for     a hydrophobic amide which is emulsified with paraffin wax using nonionic      emulsifiers; 25% solids.                                                      .sup.7 Henkel CS810, commercially available from Standard Chemical            Products; NH.sub.4 OH neutralized, 20% active in water; acid number and       softening point similar to AC ® polyethylene 680 in footnote 3.           .sup.8 Discol 738, commercially available from Callaway Chemical Company.     .sup.9 Ethylene copolymer 5120 commercially available from Allied             Corporation; acid number about 120 and a softening point of about             92° C.                                                                 .sup.10 Ethylene copolymer 540 commercially available from Allied             Corporation; acid number of about 40 and a softening point of about           108° C.                                                                .sup.11 Repellan 80 commercially available from Henkel Coporation; 40%        active emulsion; a siloxane of the comonomers dimethyl and                    3[(2-aminoethyl)amino propyl].                                                .sup.12 Discosoft 567, commercially available from Callaway Chemical          Company; 20% polyethylene emulsion, neutralized with sodium hydroxide;        similar to AC ® polyethylene 680 above.                                   .sup.13 A-C ® polyethylene 316, commercially available from Allied        Corporation; acid number of about 16 and a softening point of about           140° C.; neutralized with potassium hydroxide.                         .sup.14 A-C ® polyethylene 656 commercially available from Allied         Corporation; acid number of about 15 and a softening point of about           100° C.; neutralized with potassium hydroxide.                         *Examples of the present invention  all other comparative examples.      

                  TABLE 2                                                         ______________________________________                                        NYLON SPIN FINISH DATA                                                        Example Formulation.sup.2   % Completes.sup.1                                 ______________________________________                                        24      Same as Example 23 except 3.75                                                                    94                                                (control)                                                                             parts oxidized polyethylene                                           25      Overfinish of Example 15                                                                          31                                                26      Overfinish of Example 7                                                                           24                                                27      Overfinish of Example 22                                                                          18                                                28      50/50 Blend of overfinishes of                                                                    38                                                        Examples 24 and 25                                                    ______________________________________                                         .sup.1 Drawtwist completes, %, determined as follows. Potential packages      (PP) less the number of packages that did not start (NSP) less the number     of packages that broke out (BOP), divided by the potential packages less      the number of packages which did not start, all times 100 equals drawtwis     completes in %.                                                               ##STR2##                                                                      .sup.2 Target 0.7 to 0.9% solids on yarn.                                

                  TABLE 3                                                         ______________________________________                                        OTHER NYLON SPIN FINISH DATA                                                                         Y/M       Y/Y Wet                                                             Abrasion.sup.4,                                                                         Abrasion.sup.5,                              Example                                                                              Repellan.sup.1 /PE.sup.2, %.sup.3                                                             %         Cycles                                       ______________________________________                                        29     0.00/0.011      58.9      207                                          30     0.05/0.011      76.5      323                                          31     0.10/0.011      53.7      180                                          32     0.15/0.011      72.7      253                                          33     0.10/0.045      60.3      190                                          31     0.10/0.011      53.7      180                                          34     0.10/0.006      63.4      174                                          35     0.10/0.003      69.7      251                                          ______________________________________                                         .sup.1 See Footnote 11, Table 1.                                              .sup.2 See Footnote 3, Table 1.                                               .sup.3 On fiber.                                                              .sup.4 5 tests per sample.                                                    .sup.5 4 tests per sample.                                               

                  TABLE 4                                                         ______________________________________                                        ROPE TEST DATA                                                                                   Breaking                                                   Ex-                Strength, Lb    Abrasion,                                  am-  Finish   Linear           Retention,                                                                            Cycles                                 ple  System.sup.1                                                                           Density.sup.2                                                                          Dry  Wet  %       Dry  Wet                             ______________________________________                                        37    7       6.0      9488 8730 92      1303 409                             38   15       5.9      9970 9575 96      1363 399                             39   22       6.1      9433 8863 94      1411 394                             40    1       --       9970 --   --      --    21                                  (Control)                                                                41   36       --       --   --   --      --    61                                  (Com-                                                                         parative)                                                                ______________________________________                                         .sup.1 Represents example number.                                             .sup.2 Lbs/100 Ft  converts to kg/100 m when multiplied by 1.488.        

                  TABLE 5                                                         ______________________________________                                        PET SPIN FINISH*                                                              Components                Parts                                               ______________________________________                                        Refined Coconut Glyceride 15                                                  Hexadecyl Stearate        15                                                  POE (4) Lauryl Alcohol    13                                                  Sodium Petroleum Sulfonate, 60-62% active in                                                            10                                                  mineral oil                                                                   POE (20) Ethoxylated Tallow Amine                                                                        5                                                  Sodium Salt of Sulfonated Succinic Acid                                                                  2                                                  Mineral Oil, 40 SSU Viscosity                                                                           40                                                  Total                     100                                                 ______________________________________                                         *Applied at 0.2% solids add on.                                          

                  TABLE 6                                                         ______________________________________                                        PET OVERFINISH DATA                                                                        Y/Y     Y/M                                                                   Abrasion,                                                                             Abrasion Finish, %                                       Ex-                Cycles    %      Add  Reten-                               ample Formulation.sup.1                                                                          Wet.sup.2                                                                            Dry.sup.3                                                                          Wet    On   tion.sup.4                         ______________________________________                                        *42   Overfinish   100    452  85     0.52 25                                       of Example 2                                                            *43   Paraffin wax.sup.5                                                                         345    452  95     0.48 38                                       (melts at 54.4° C.)                                                    + polyethylene.sup.6                                                    44    Overfinish   452    452  93     0.53 70                                       of Example 7                                                            45    Overfinish   452    452  93     0.50 95                                       of Example 15                                                           46    Overfinish   452    452  85     0.47 85                                       of Example 22                                                           ______________________________________                                         .sup.1 Applied by kiss roll from 10% solids aqueous emulsions.                .sup.2 1000 g pretension weight.                                              .sup.3 600 g pretension weight.                                               .sup.4 Footnote 2, Table 1.                                                   .sup.5 Repelotex D, commercially available from Lyndal Chemical.              .sup.6 Discosoft 567, see Table 1.                                            *Comparative examples.                                                   

We claim:
 1. A method of producing a wet abrasion resistant cordage fromyarn comprising:treating the yarn after drawing with an effective amountof an aqueous overfinish composition having an oil portion whichcomprises about 20 to 80 weight percent of an oxidized polyethyleneemulsified with a non-nitrogen nonionic emulsifier and neutralized withan alkali hydroxide; and about 80 to 20 weight percent of a compoundselected from the group consisting of a siloxane of the comonomersdimethyl and 3-[(2-aminoethyl)aminopropyl], and an amide melamine waxthen forming said cordage.
 2. The method of claim 1 wherein said yarn istreated with a sufficient amount of said composition to achieve at leastabout 0.25 weight percent oxidized polyethylene on the yarn.
 3. Themethod of claim 2 wherein said compound is the siloxane and wherein saidyarn is treated with a sufficient amount of said composition to achieveat least about 0.25 weight percent siloxane on the yarn.
 4. The methodof claim 3 wherein said yarn is polyester.
 5. The cordage made accordingto the method of claim
 4. 6. The method of claim 3 wherein said yarn ispolyamide.
 7. The cordage made according to the method of claim
 6. 8.The method of claim 3 wherein said yarn is polyolefin.
 9. The cordagemade according to the method of claim
 8. 10. The method of claim 2wherein said compound is the amide melamine wax and wherein said yarn istreated with a sufficient amount of said composition to achieve at leastabout 0.25 weight percent wax on the yarn.
 11. The method of claim 10wherein the amide melamine wax is formed by reacting melamine with a C₆to C₃₆ fatty acid to form a hydrophobic amide which is emulsified withparaffin wax using nonionic emulsifiers.
 12. The method of claim 11wherein the melamine is reacted with a C₁₀ to C₁₈ fatty acid.
 13. Themethod of claim 12 wherein said yarn is polyester.
 14. The cordage madeaccording to the method of claim
 13. 15. The method of claim 12 whereinsaid yarn is polyamide.
 16. The cordage made according to the method ofclaim
 15. 17. The method of claim 12 wherein said yarn is polyolefin.18. The cordage made according to the method of claim
 17. 19. The methodof claim 1 wherein the relative amounts of the oxidized polyethylene andthe compound are about the same in said composition.